Dyestuffs of the triarylmethane series



Patented May 5, 1936 UNITED STATES DYESTUFFS OF THE TRIARYLMETHANE SERIES Ottmar Wahl, Leverkusen-I. G. Werk, Ernst Teupel,

Leverkusen Wiesdorf,

and Karl Schmidt, Cologne-Mulheim, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application May 23, 1934, Serial No. 727,200. In Germany June 3, 1933 8 Claims.

The present invention relates to new dyestuffs of the triarylmethane series, more particularly it relates to dyestuffs of the general formula:

[Tlamai wherein T stands for the radical of a dyestuff of the triarylmethane series containing at least one sulfonic acid group, the group being attached to an aromatic nucleus in p-position to the carbinol C-atom, R stands for an 20 arylene radical, :2: stands for hydrogen or an HOaS @CHz-IL' acyl group, such as acetyl or benzoyl, and the groups 3' H a standing in or p-position to each other. 40 HOaS Our new dyestuffs are obtainable by starting with such dyestuffs of the triarylmethane series as contain a replaceable atom or group in p-position to the carbinol C-atom, for instance, a

halogen atom, an alkoxy group, the sulfonic acid group or the nitro group, and reacting upon the same with an 0- or p-arylenediamine. These dyestuffs of the above-identified formula, in which a: stands for an acyl group, are obtainable by acylating the dyestufis obtained in accordance with the above described process, those containing the acylamino group in p-position also. being obtainable in one step by performing the condensation with a mono-acyl-p-arylenediamine.

Our new dyestuffs are in form of their alkali metal salts generally dark, lustrous powders, dyeing the animal fibre generally greenish-blue to reddish-violet shades of good fastness to light and dischargeability.

The invention is illustrated by the following examples, without being limited thereto:

Example 1 300 parts by weight of the dyestuff of the following formula:

H502 CaHs Hi0 CH:

dyes wool and silk clear blue shades; the dyeings on silk can be discharged to a pure White.

The dyestufi obtained in accordance with paragraph 1 is stirred in the cold for 3 hours with do acetic anhydride. The excess acetic anhydride is decomposed with water, and the dyestuff obtained having in the free state the following formula:

CzHs

dyes wool and silk more greenish shades.

Example 2 300 parts by Weight of the starting dyestufi of Example 1 are molten together with 400 parts by weight of p-phenylenediamine, as described in Example 1. A dyestuif, dyeing wool and silk more greenish-blue shades and exerting otherwise the same properties is thus obtained. In its free state the dyestufi corresponds to the following formula:

Example 3 300 parts by weight of the starting dyestuff of Example 1 are molten together with 400 parts by weight of monoacetyl-p-pheny1enediamine, as described in Example 1. The dyestufi thus obtained having in the free state in the carbinol form the following formula:

NIP-00GB:

has properties similar to those of the dyestufl obtained in accordance with Example 2.

By substituting the mono-acetyl-p-phenylenediamine by an equivalent quantity of monobenzoyl-p-phenylenediamine, a dyestufl having similar properties is obtained.

Example 4 disappeared. The dyestuff which is obtained 300 parts by weight of the starting dyestufi of after separating the excess p-phenylenecliamme,

Example 1 are molten together with 400 parts and WhlCh corresponds in the free state m the 5 by Weight of 1,2 diamno 4 ethoxybenzene; the carbmol form to the following formula: 5

dyestufi thus obtained having in the carbinol dyes wool and silk clear blue shades; the dyeings form in the free state the following formula: (in silk can be discharged to a P e- 20 Hols SOJH 2E -0H,N, N-OHQ r r OH do (11 HIC" I HI GHl has the same properties as the dyestuif obtained Example 6 40 in accordance w Example 300 parts by weight of the dyestufl having the following formula:

I N H 45 Ho.s-0.H.cH=

(l)H CH:--CoH SOaH 0 E30 CH: 50

Example 5 are heated at 100 C. with 400 parts by weight of 3 parts by weight of the dy tufl correspond o-phenylenediamine, until the green dyestuif has m t the following formul disappeared. The dyestuff purified dyes wool and 60 C:H|\ /C:H|

N i N\ nols-oair-on/ E CHr-C H BO|H 65 are heated at 100 C. with 400 parts by weight of silk violet shades of good fastness to light and p-phenylenediamine, until the blue dyestufi has dischargeability. In the carbinol form the dye- 75 stuff corresponds in the free state to the following formula:

H1O CH:

Example 7 300 parts by weight of the dyestuff having the following formula:

CH: CH:

H N NH:

are heated at 100 C. with 400 parts by weight of o-phenylene-diamine, until the bluish-green dyestuff has disappeared. The dyestuff which is obtained after separating the excess diamine having in the carbinol form in the free state the following formula:

CH: CH:

HzN NH:

OH H1O i CH: C

dyes wool and silk clear, reddish-violet shades of good fastness to light and dischargeability.

By after-treating the dyestuff with a sulfonating agent, such as concentrated sulfuric acid, a sulfonic acid group enters the phenyl nucleus of the phenylenediamine radical, thereby rendering the dyestuif more easily soluble; this sulfonated dyestufi exerts otherwise the same properties.

A bluish-violet dyestuff is obtained by melting the dyestuff of this example with p-phenylenediamine sodium sulfonate. In the carbinol form the dyestuif corresponds in the free state to the following formula:

By melting together the starting dyestuif of this example with 1,2-diaminobenzene-4-carboxylic acid, there is obtained a dyestuff having in the carbinol form in the free state the following formula:

(3H1 ICH:

HzN- NH:

H BIC I C C COOH dyeing wool and silk clear reddish-violet shades.

By melting together the starting dyestuff of this example with 1,2-diaminonaphthalene-5-sul-- Ionic acid, there is obtained a dyestufi having in dyeing wool and silk clear reddish-violet shades.

By melting together the starting dyestufl of this example with 1.4-naphthylenediamine and sulfonating the product, there is obtained a dyestuff having in the carbinol form in the free state the following formula:

CH: CH!

HIN NH| 011 111C CH: C

dyeing wool and silk clear violet shades.

Example 8 300 parts by weight of the dyestufl of the following formula:

Echo-I ium} t H l -SO.H

are heated at 100 C. with 400 parts by weight of o-phenylenediamine, until the greenish-blue dyestufi has disappeared. The blue dyestufl which is obtained after separating the excess diamine and which corresponds in the carbinol form in the free state to the following formula:

dyes wool and silk clear blue shades; the dyeings on silk can be discharged to a pure white.

We claim:

1. Triarylmethane dyestuffs of the general formula H l... R N

wherein T stands for the radical of a dyestufl. of the diamine triarylmethane series containing at least one sulfonic acid group, the group being attached to an aromatic nucleus in p-position to the carbinol C-atom, R stands for an arylene radical, :2: stands for hydrogen or an acyl group, and the groups /H NH and --N\ stand in 0- or p-position to each other, dyeing the animal fibre generally greenish-blue to reddish-violet shades of good fastness to light and dischargeability.

2. Triarylmethane dyestufis oi the general formula:

NH-RN I J wherein T stands for the radical of a dyestuf! of the diamino triarylmethane series containing at least one sulfonic acid group, the group stand in or p-position to each other, dyeing the animal fibre generally greenish-blue to reddishviolet shades of good fastness to light and dischargeability.

I 3. Triarylmethane dyestufis of the general wherein T stands for the radical of a dyestuff of the diamino triphenylmethane series containing 35, ,at least one sulfonic acid group, the group being attached to a benzene nucleus in p-position to the carbinol C-atom, R stands for an arylene radical, mstands for hydrogen or an acyl group, and the groups stand in 0- or p-position to each other, dyeing the animal fibre generally greenish-blue to reddish-violet shades of good fastness to light and dischargeability.

4. Triarylmethane dyestuffs of the general formula:

lNW

65 wherein stands for the radical of a dyestufi of the diamino triphenylmethane series containing at least one sulfonic acid group, the groupbeing attached to a benzene nucleus in p-position 75 -to thecarbinol C-atom, R stands for an arylene radical of the benzene or naphthalene series, as stands for hydrogen, an acetyl group or benzoyl group, and the groups stand in 0- or p-position to each other, dyeing the animal fibre generally greenish-blue to reddishviolet shades of good fastness to light and dischargeability.

5. Triarylmethane dyestufis having in the carbinol form the following general formula:

wherein R1 and R2 stand for radicals of the henzene series, R1 bearing in p-position to the carbinol C-atom an amino group, the hydrogen atoms of which may be substituted by substituents selected from the group consisting of alkyl, aralkyl and aryl, R stands for an arylene radical of the benzene or naphthalene series, the group being attached to R2 in p-position to the carbonol C-atom, :0 stands for hydrogen or an acyl group, the groups standing in 0- or p-position to each other, and wherein the molecule contains at least one sulfonic acid group, dyeing the animal fibre generally greenish-blue to reddish-violet shades of good fastness to light and dischargeability.

6. The dyestufi having in the carbinol form in the free state the following formula:

C H: C H:

HzN I NH;

HaC ()H CH: C

HOzS

dyeing wool and silk clear reddish-violet shades of good fastness tolight and dischargeability.

7. The dyestuff having in the carbinol form in the free state the following formula:

CH: CE:

SOIH 10 OSOIH 15 dyeing wool and silk bluish-violet shades of good tastness to light and dischargeability.

CHI

8. The dyestufi having in the carbinol form in the free state the following formula:

2 2 HOlS E! HI 

